Materials Research.

2014; 17(3): 570-582 © 2014

DDOI: http://dx.doi.org/10.1590/S1516-14392014005000054

Comparative Study of the Characteristics of Nano Silica–,

Silica Fume– and Fly Ash–Incorporated Cement Mortars

Hasan Biricika, Nihal Sarierb*

a
Department of Civil Engineering, Maltepe University, Marmara Campus, 34857, Maltepe, Istanbul, Turkey
b
Department of Civil Engineering, Istanbul Kültür University, Atakoy Campus,
34156, Bakirkoy, Istanbul, Turkey

Received: June 3, 2013; Revised: December 9, 2013

The structural characteristics of cement mortars, impregnated with nano silica (NS), silica fume
(SF) and fly ash (FA), were comparatively studied using Fourier transform infrared spectrometer
(FTIR), thermogravimeter-differential thermogravimeter (TG-DTG) and scanning electron microscope
(SEM). The mechanical strengths of the specimens were determined at early (7th day) and standard
(28th day) curing ages. The compressive strengths and flexural strengths developed in the mortar
specimens containing NS particles were found considerably higher than those of the corresponding
specimens of SF and FA over and above the control at both ages. FTIR, TG-DTG and SEM analyses
results were consistent with the remarkable increase in the mechanical strength of the mortars with NS.
These increases in the strengths of the mortars with NS are attributable to the nano sized particles and
extensive surface area of NS. The nano sized particles, as nucleating agents, promoted the hydration of
C3S and C2S and the formation of C–S–H phase. Plenty of active sites on the surface of NS particles
induced their pozzolanic reactivity and the extent of bond formation between NS particles and free CH.

Keywords: nano silica, silica fume, fly ash, mortar, FTIR, TG–DTG

1. Introduction
The cement industry is considered to be one of the most
energy consuming industries, which is also responsible
for approximately 6-7% of the global man-made CO 2
emissions annually1-4. Accordingly, there is a great demand
to minimize the quantity of cement used in the construction
industry 4. In this context, supplementary cementing
materials (SCMs) with pozzolanic or hydraulic properties
have been particularly attractive compounds or mixtures
which partially replace ordinary Portland cement required
for a cement-based composite5,6. The most widely used
SCMs in cement composites are fly ash (FA) and silica fume
(SF), that are obtained as the by-products of the coal industry
and the silicon-ferrosilicon industries, respectively7,8.
FA and SF enhance mainly the long-term strength and
durability properties of cement composites owing to their
pozzolanic reactions with calcium hydroxide formed during
the hydration of calcium silicates7-11. However, there are
some concerns about cement composites incorporated with
FA or SF. For example, the strength development of FA
concrete, particularly that containing Class F fly ash, is slow
compared to normal concrete that is not suitable for many
applications where early strength is required, such as repairs
and rapid construction5,6. Whereas, concretes containing SF
are thought to be more susceptible to plastic shrinkage than
any other type of concrete, particularly in structures with
large surface areas12.
Recently, impregnation of nanoparticles into ordinary
Portland cement (OPC) paste, mortar and concrete has
*e-mail: n.sarier@iku.edu.tr
received particular attention as a promising research
field for nanocomposites, which can produce superior
mechanical and physical properties in OPC composites.
This nanocomposite technology can be applied directly to
the construction industry13. Previous research indicates that
the inclusion of nanoparticles improves fresh and hardened
state properties, even when compared with conventional
mineral additions13-15. Among these nanoparticles, nano SiO2
(nano silica, NS) is becoming an increasingly important
component of special concretes and other advanced cement
based materials8,15-26. It consists of amorphous silicon dioxide
with a particle size at nano scale, having a high surface
area to volume ratio, therefore providing the potential for
tremendous chemical reactivity1,2,14. Currently, the prices of
various NS products in the markets are higher than FA and
SF which limit their commercial applications27. However,
some latest studies have focused on developing new
processes for reducing the raw material, energy consumption
and cost in NS production27,28.
Many research groups have conducted experiments
on the microstructure, mechanical and physical properties
of cement paste, mortar and concrete impregnated with
NS[1,15-17]. These experimental studies have shown that NS
causes great enhancement in compressive and flexural
strengths, durability, modulus of elasticity, pore structure
and resistance to ion penetration, and setting time of cement
based materials8,15-26. When NS particles are included into
hydrating OPC, they increase calcium silicate hydrate
(C–S–H) gel formation as a result of the reaction of NS
with Ca(OH)2 (calcium hydroxide, CH), accelerate the
2014; 17(3) Comparative Study of the Characteristics of Nano Silica–, Silica Fume– and Fly Ash–Incorporated Cement Mortars 571

hydration of tricalcium silicate (C3S) and dicalcium silicate
(C2S) and fill spaces in the C–S–H crystal lattice, acting as
a nano-filler16,21,29. Furthermore, NS decreases the setting
time of mortar and reduces bleeding water and segregation
while improving the cohesiveness of mixtures in the fresh
state29. On contrary, there are two important problems to be
considered regarding use of NS in cement composites. One
important difficulty is dispersing NS particles in a cement
mixture. The previous studies showed that the dispersion
method of the NS particles affects the workability of cement
mortar, the rate and extent of cement hydration as well as the
structural, physical and mechanical properties of the fresh
and hardened cement composites11,30-33. Some authors have
concluded that the appropriate percentage of NS must be
small (1-5 wt%) to avoid agglomeration of particles during
mixing12-16, while others have indicated that properties can
also be improved with higher dosages up to approximately
10 wt% if these nanoparticles are successfully dispersed
in the initial cementious mixture7,12,17,29. Second problem
related with using NS in a cement mixture is the decrease
in fluidity, due to its high surface area and increased
water demand29-34. Some research groups have studied the
interaction of superplasticizers with NS added cements, and
reported that the type and concentration of superplasticizer,
along with the particle size and surface area of NS, affect
the rheological properties of fresh cement mixtures29-34.
Very recently, the effects of morphological and textural
characteristics of different amorphous nano silica’s on
mechanical properties of standard mortars were studied, and
the main parameters influencing the mechanical properties
of cement mortars were reported as the specific surface area,
the micropore volume and the average size of the primary
particles of the silicas28,35. In the view of all these intensive
studies, it sounds that developing and characterization
of new NS based cement composites with improved
mechanical performance and durability continue to draw
attention as an open-ended research topic for promoting
the appropriate use of nano silica at the industrial scale in
construction sector.
In the present study, the achievability of using 5 wt%
and 10 wt% of NS to reduce cement consumption in mix
proportions of cement mortars while improving their
mechanical strength was investigated. The influence of the
high dosages of NS on the compressive and flexural strengths
and structural properties of cement mortars at early (7th day)
and standard (28th day) curing ages were compared with
the effect of equal amounts of SF and FA. The structural
changes of mortar specimens were characterized by Fourier
transform infrared spectrometer (FTIR), thermogravimeter-
differential thermogravimeter (TG-DTG) and scanning
electron microscope (SEM).
2. Experimental
2.1. Materials
Nano SiO2 (Silicon dioxide 4850MR® or NS) in powder
form was purchased from NanoAmor, Inc. (Houston, TX).
A specific gravity of 2.2-2.4 at 25 °C, bulk density of
0.068 g.mL–1, average particle size of 15 nm and specific
surface area of 640 m2.g–1 were the listed physical properties
of this batch of NS[36]. The silica fume (SF) and the F type
fly ash (FA) were from Eti Krom Inc. (Istanbul, TR) and
Yatagan Thermal Plant (Yatagan, TR), respectively. The
particle size distributions of SF and FA were measured
with a Malvern Nanosizer ZS3600 at λ=633 nm, using
0.01% dilute SF and FA suspensions in isopropyl alcohol
at 25 °C. Multipoint BET surface area measurements of SF
and FA were conducted using a Quantachrome Nova4000E
at 77.3 K with nitrogen as the adsorbent gas. The particle
size, specific surface area and specific gravity values of NS,
SF and FA are listed in Table 1. The SEM images of NS, SF
and FA used in this study are shown in Figure 1.

Table 1. The chemical compositions of OPC, NS, SF and FA as reported by the suppliers and their specific gravity, mean particle size
and specific surface area (BET) values.
Constituents Content (wt%)
OPC NS SF FA
SiO2 20.6 99.5 83.9 56.3
Al2O3 4.5 <0.004 0.5 32.1
Fe2O3 3.2 <0.001 1.3 3.9
Na2O 0.3 – 0.5 0.1
K2O 0.8 – 2.9 -
CaO 64.0 <0.003 1.4 3.9
MgO 1.2 <0.002 4.8 1.4
Cr2O3 0.3 – 0.6 –
SO3 3.1 – 1.3 –
Loss on ignition at 1000 °C 1.4 2.5 2.2
Physical properties
Property OPC NS* SF FA
Specific gravity (at 25 °C) 3.14 2.20-2.40 2.21 2.20
Mean particle size (nm) 15.5×103 15.0 444.2 1513.0
BET surface area (m2.g–1) (±0.05) 3.99×10–1 640.00 13.90 2.60
*Listed properties provided by the supplier’s data sheet36
572 Biricik & Sarier Materials Research

Ordinary Portland cement (OPC) with a specific gravity
of 3.14 and classified using the TS EN 197-1 standard
was obtained from Akcansa Cement Inc. (Istanbul, TR).
Commercial silica sand with a maximum particle size of
2.0 mm, specific gravity of 2.63 and fineness modulus
of 2.91, was purchased from Pınarhisar Cement Inc.
(Kırklareli, TR) and used as an aggregate in the mortar.
The superplasticizer admixture, prepared as defined in the
CSN EN 934-2 standard37, was polycarboxylic acid based
(Sika® ViscoCrete® Hi-Tech 32) with a density between
1070 and 1110 kg.m–3, an alkali content of less than 4% of
Na2O, and a chloride ion content of less than 0.1%. The
chemical compositions of OPC, NS, SF and FA reported
by the suppliers are given in Table 1.
2.2. Preparation and characterization of the
cement mortar specimens
To obtain colloidal dispersions of NS, SF or FA, a
known amount of the additive was mixed with 225 g of
distilled water and stirring was performed at 15,000 rpm
with IKA T 25 digital Ultra-Turrax® Homogenizer for
2 min at room temperature. Consequently, the physical
attractions between NS, SF or FA particles were overcome
and new physical attractions, especially hydrogen bonding
between O atoms of SiO2 and OH groups of water molecules
were obtained, which triggered the pozzolanic reactivity
of the particles8,16,20. For each sample, a known amount of
polycarboxylic acid based superplasticizer was added into
the colloidal dispersion over 30 s at 120 rpm to prevent
flocculation and water entrapment in the flocks, reducing the
amount of water needed to obtain comparable fluidity32,33.
The mixture was left to rest for 1.5 min and then stirred
further at 120 rpm for 1 min. Next, a known amount of
cement and 350 g of sand were added to the dispersion
while stirring at 120 rpm for 1 min. Each mixture was
instantly poured into a stainless steel mold (40 mm × 40 mm
× 160 mm) on a vibrator plate enabling compaction. One
day later, the demolded mortar specimens were cured in a
lime-saturated water bath at 20±2 °C until they were tested.
The cement mortars were prepared with water to cement
ratio of 0.5. In order to achieve a constant workability,
the appropriate amounts of water and superplasticizer to
be added into a mortar mixture, were predetermined by
measuring the mean diameter (R´) of a test sample on flow
table according to CEN EN 1015-3 standard38. The flow
tests were repeated, using a fresh batch of mortar each time,
until the desired flow was achieved. Table 2 illustrates the
mixture proportions, spread ratios and bulk densities of the
mortar specimens.

Figure 1. SEM images taken in this study for the pozzolanic additives: a) NS, magnification x5,000; b) SF, magnification x5,000; and
c) FA, magnification x2,000.

Table 2. Mixture proportions, spread ratios and bulk densities of the mortar specimens (water to cement ratio =0.50).
Sample Type and amount of Amount of Amount of Spread ratio (R´/100) Bulk density
mineral additive superplasticizer (g) cement (g) (kg.dm–3)
OPC - 0.0 450.0 1.00 2.16
NS5 22.5 g NS 5.0 427.5 1.03 2.13
(5 wt%)
NS10 45.0 g NS 10.0 405.0 1.00 2.12
(10 wt%)
SF5 22.5 g SF 1.0 427.5 1.00 2.14
(5 wt%)
SF10 45.0 g SF 2.0 405.0 1.00 2.13
(10 wt%)
FA5 22.5 g FA 1.0 427.5 1.00 2.15
(5 wt%)
FA10 45.0 g FA 2.0 405.0 1.00 2.14
(10 wt%)
2014; 17(3) Comparative Study of the Characteristics of Nano Silica–, Silica Fume– and Fly Ash–Incorporated Cement Mortars
Compressive and flexural strength experiments of the
specimens were performed at early and standard curing ages
according to ASTM C39/C39M–12 and ASTM C348–08
Standards39,40, respectively, using a FORE FR–BC293–type
united testing system equipped with 20 kN and 200 kN load
cells, respectively, and attached to a computer interface for
data acquisition. The loading speed was 0.24 MPa.s–1.
Changes in the structure of the mortar specimens,
including those with 10 wt% NS, SF or FA, were examined
with a Perkin Elmer Spectrum 100 Fourier transform infrared
spectrometer (FTIR) equipped with a universal attenuated
total reflection (ATR) accessory. Thermogravimetric and
differential thermogravimetric (TG-DTG) analyses of the
samples were performed from 20 to 1000 °C at 10 °C.min−1
rate under a dry nitrogen atmosphere purged with a SEIKO
6200 TG/DTA instrument at 20 mL.min−1 rate. The TG/
DTA instrument was calibrated with indium, and platinum
pans were used as sample holders. For TG-DTG analysis,
a sample was taken from the center of each specimen, then
grinded into a powder. The approximate sample mass was
100 mg per sample. TG-DTG experiments were repeated
for three different samples of each specimen. Scanning
electron microscopy (SEM) analyses were performed using
a JEOL JXA840A type SEM instrument. For preparation of
the SEM samples, approximately 0.01 g of a sample taken
from the middle of each mortar specimen was placed on
standard mounts 15 mm in diameter and 2 mm in depth under
Figure 2. Compressive strength of the mortar specimens versus
days of hydration: a) the specimens with 5 wt% mineral additive
and the control; b) the specimens with 10 wt% mineral additive
and the control.
573
a vacuum and coated with a 1-2 nm thick conductive layer
of gold to prevent charging prior to imaging. The applied
voltage and current values were 40.0 kV and 30.0  mA,
respectively.
3. Results and Discussion
3.1. Mechanical strength results
Compressive and flexural strength data for all of the
specimens as a function of the extent of hydration are
presented in Figure  2 and 3, respectively. As given in
Figure 2a, the compressive strength of OPC was 28.7 MPa
after 7 days of curing. At early age, the compressive
strength of the NS5, SF5 and FA5 specimens with 5 wt%
mineral additives was 31.4 MPa, 28.5 MPa and 22.7 MPa,
respectively. The compressive strength of NS5 was 9.5%
greater than that of OPC. Conversely, 5 wt% mineral
addition in SF5 and FA5 did not result in improvement in the
compressive strength in comparison to OPC after 7 days of
curing. That is to say, the compressive strength of SF5 was
very close to that of OPC while the compressive strength of
FA5 was lower than that of OPC at early age. After 28 days
of curing, the compressive strength of OPC was measured
as 31.9 MPa. At this standard age, the compressive strength
of the NS5 and SF5 specimens ascended to 41.9 MPa
and 39.6  MPa, and the corresponding increases in their
Figure 3. Flexural strength of the mortar specimens versus days
of hydration: a) the specimens with 5 wt% mineral additive and
the control; b) the specimens with 10 wt% mineral additive and
the control.
574 Biricik & Sarier
compressive strength, compared to OPC, were calculated
to be 32% and 24%, respectively. On the contrary, the
compressive strength of FA5 was measured 30.4 MPa at the
age of 28 days, which was slightly lower than that of OPC.
As seen in Figure  2b, when the amount of mineral
additive was increased to 10 wt%, in the NS10, SF10 and
FA10 specimens, compressive strengths reached 38.7 MPa,
33.9 MPa and 30.6 MPa, respectively, at 7 days. These
increases in the compressive strength of NS10, SF10 and
FA10, compared to OPC, were calculated as 35%, 18% and
7% respectively. After 28 days of curing, the compressive
strength of NS10, SF10 and FA10 increased to 58.5 MPa,
45.9 MPa and 37.6 MPa, respectively. The corresponding
increases in the compressive strength of NS10, SF10 and
FA10, compared to that of OPC, were calculated as 84%,
44% and 18%, respectively.
As seen in Figure  3a, the flexural strengths of the
specimens with 5 wt% mineral additive (NS5, SF5 and
FA5) were in the range of 6.1 MPa–6.3 MPa, which were
slightly higher than that of OPC (6.0 MPa) at early age.
After 28 days of curing, the flexural strength of the mortar
specimen NS5, with 5 wt% NS, ascended to 7.5 MPa, while
the flexural strengths of the SF5 and FA5 specimens were
approximately 6.5 MPa, on par with OPC (6.3 MPa) (see
Figure 3a). The flexural strength of NS5 was 19% higher
than that of OPC at standard age.
The flexural strengths of the specimens with 10 wt%
mineral additive (NS10, SF10 and FA10), given in Figure 3b,
were in the range of 6.3 MPa–6.9 MPa, which were slightly
higher than that of OPC (6.0 MPa) after 7 days of curing.
On the other hand, after 28 days, the flexural strength of
NS10, with 10 wt% NS, increased to 8.3 MPa, while the
flexural strengths of SF10 and FA10 with 10 wt% SF and
FA additives were measured as 7.5 MPa and 6.5 MPa,
respectively. The flexural strength of NS10 was the highest
Figure 4. FTIR transmission spectra of the mortar specimens containing 10 wt% of NS, SF and FA after 7 days (… dashed line) and
28 days (– solid line) of curing.
Materials Research
across all the specimens and 32% higher than that of OPC
at standard age.
3.2. Characterization of the mortar specimens
FTIR transmission spectra of the mortar specimens,
including 10 wt% of NS, SF and FA after 7 days and 28
days of curing, are presented in Figure 4.
The broad bands appearing at 3648-3650 cm–1 in the
spectra of all mortar specimens including OPC (control)
corresponded to the overlapping stretching vibrations of
the structural –OH groups (ν3) of Ca(OH)2 formed during
the hydration of C3S and C2S, and the free –OH groups
(ν1) of water molecules present in the mixture41,42. This
band diminished for all samples as the hydration process
proceeded, implying a decrease in free water due to C–S–H
bond formation43. The decrease in the intensity of this band
for NS10 and SF10 were the most pronounced after 28 days
of hydration. Furthermore, the 3650 cm–1 band of NS10
had nearly disappeared, suggesting increased consumption
of C3S and C2S phases and also increased formation of
C–S–H phase compared to SF and FA, over and above the
pozzolanic reactivity of NS for Ca(OH)2[1].
The broad band observed at 3411 cm–1 in the IR spectra
of OPC corresponded to overlapping stretching vibrations
of both the structural and free –OH groups of CH, C–S–H
and water, respectively1,41. The intensity of the 3411 cm–1
band of OPC did not change after 28 days of curing, while
that of FA10 decreased a little. This band shifted slightly to
3410-3390 cm–1 and became broader and smaller in the IR
spectra of the NS10 and SF10 specimens. This phenomenon
indicated a decrease in the amount of bonded –OH groups
and free water, signifying reduction in Ca(OH)2 content, and
increase in C–S–H content in NS10 and SF10[1,41-44]. The
bending-in-plane vibrations of the –OH groups (ν2) of free
water molecules are characterized by a small broad band
2014; 17(3) Comparative Study of the Characteristics of Nano Silica–, Silica Fume– and Fly Ash–Incorporated Cement Mortars 575

at 1671 cm–1. Similar to the stretching vibrations, this band
had lower intensities in the spectra of the NS10 and SF10
specimens compared to the OPC and FA10 samples after
28 days, confirming the decrease in free water due to C–S–H
formation, which occurred faster than in OPC and in FA10[1].
The FTIR spectrum of OPC showed two distinct peaks
at 1420 cm–1 and 873 cm–1, corresponding to the stretching
and bending-in-plane vibrations of the C–O bonds of CH
and CaCO3, resulting from the reaction between Ca(OH)2
and CO2 in the air45-47. The intensity of the 1420 cm–1 band
is assumed to be closely related with the ratio and depth
of carbonation46,47. The 1420 cm–1 band shifted slightly to
1412-1419 cm–1 in the FTIR spectra of the NS10, SF10 and
FA10 specimens after 7 days and 28 days of curing. The
intensities of the 1412-1419 cm–1 band of NS10 and SF10
were smaller than that of FA10 and the control at standard
age suggesting the decrease in carbonation ratio and depth
in these samples45-47. Similar to the stretching vibrations, the
bending-in-plane vibrations of the C–O bonds at 873 cm–1
had lower intensities in the IR spectra of the NS10 and SF10
specimens at standard age46.
The band appeared at 1120 cm–1 in the FTIR spectrum
of OPC, corresponding to the stretching vibrations of the
S–O bond of gypsum and ettringite44,47. This band decreased
in size as the curing time was extended in the spectra of
FA10, SF10 and specifically in the FTIR spectrum of NS10
after 28 days reminding lesser extent of ettringite formation
in NS10[44,46,47]. The strong band observed at 949 cm–1 and
the band observed at 719 cm–1 were associated with the
bending-in-plane vibrations of the Si–O bonds in tricalcium
silicates (C3S) and dicalcium silicates (C2S)[1,40,42,47]. The
intensity of these bending–in–plane vibrations of the Si–O

Figure 5. At the age of 7 days: a) TG and b) DTG curves of the mortar specimens containing 10 wt% of NS, SF and FA.
576 Biricik & Sarier
bonds decreased as C–S–H crystals formed48. The intensities
of the 949 cm–1 band of OPC after 7 days of curing and
28 days of curing overlapped, indicating deceleration of
C–S–H formation as the curing time was prolonged in OPC.
Addition of NS, SF or FA into the cement mortar influenced
the positions and intensities of these Si–O bending
vibrations. The 949 cm–1 band shifted to 969-972 cm–1 and
the 719 cm–1 band shifted to 730 cm–1 in the FTIR spectra
of NS10, SF10 and FA10 after 7 days and 28 days, which
have been defined as a fingerprint evidence for the degree
of polymerization with the formation of C–S–H phase due
to hydration1. The intensities of the Si–O bending bands of
NS10 and SF10 after 28 days of curing dropped noticeably,
while those of OPC and FA10 did not change significantly.
These findings were further evidences for the polymerization
of the silica groups and formation of C–S–H bonds in NS10
and SF10 as curing time was extended to 28 days48. After
28 days of curing, the lowest intensities were observed for
the Si–O bending bands of the NS10 specimen, highlighting
the highest degree of polymerization silica (SiO4) units with
Figure 6. At the age of 28 days: a) TG and b) DTG curves of the mortar specimens containing 10 wt% of NS, SF and FA.
Materials Research
the formation of C–S–H phase in NS10 compared to OPC,
FA10 and even to SF10[19,48].
Figure 5a, 5b and Figure 6a, 6b present TG and DTG
curves of the mortar specimens containing 10 wt% of NS,
SF and FA after 7 days and 28 days of curing, respectively.
TG-DTG curves show the typical reactions occurring in the
cement mortars when subjected to a progressive temperature
increase from room temperature to 1000 °C. The mass
loss in the mortar specimens, including the control, during
heating in the TG-DTG analyses occurred in three main
steps. The dehydration of water molecules in hydrates
such as C–S–H and ettringite took place within the range
from room temperature to 200 °C[29,49-55]. The second step
of thermal degradation occurred between 325-550 °C,
and the corresponding mass loss was associated with the
dehydroxylation of free CH produced during curing29,49-55.
When the mortar specimens were cured, calcium hydroxide
forming in them gradually combined with carbon dioxide of
the surrounding air to form calcium carbonate46. The third
decomposition step happened between 550-740 °C was due
2014; 17(3) Comparative Study of the Characteristics of Nano Silica–, Silica Fume– and Fly Ash–Incorporated Cement Mortars 577

to decomposition of calcium carbonate and escape of CO2
from the cement matrix46,49-57. Table 3 presents the mass
percent of free CH, and the mass percent of CaCO3 which
were calculated by multiplying the mass loss percent of the
second and third steps of TG curves, given in Figure 5a and
5b, with the stoichiometric molar mass ratios of Ca(OH)2/
H2O and CaCO3/CO2, respectively, as mentioned in the
literature46,56,57.
At the age of 7 days, the TG curves of FA10, SF10 and
NS10 showed similar changes to that of OPC, with some
changes in mass loss and mass loss rates at each step. The
first DTG peaks of OPC after 7 days of curing appeared at
62 °C and 89 °C, corresponding to a 13% mass loss on the
TG curve up to 200 °C. Similarly, the first DTG peaks of
FA10, SF10 and NS10 appeared between 61 °C and 93 °C
in which the highest mass loss rates were observed for NS10

Table 3. Mass % of Ca(OH)2 and of CaCO3 calculated from the second and third steps of TG analyses for the mortar specimens containing
10 wt% of NS, SF and FA at the age of 7 days and 28 days.
Sample Second step of TG Third step of TG Sum of second and third steps of TG
Mass% of Ca(OH)2 Mass% of CaCO3 Total mass% of Ca(OH)2 and CaCO3
7 days 28 days 7 days 28 days 7 days 28 days
OPC 15.2 20.6 13.6 5.2 28.8 25.8
FA10 14.4 18.1 6.8 7.7 21.2 25.8
SF10 13.2 16.4 5.2 7.3 18.4 23.7
NS10 9.9 14.0 7.5 5.4 17.4 19.4

Figure 7. SEM images of the mortar specimens after 7 days of curing: a) OPC (control), magnification x10,000; b) NS10, magnification
x7,500; c) SF10, magnification x5,000; d) FA10, magnification x10,000.
578 Biricik & Sarier Materials Research

and SF10. The mass loss on the TG curves of FA10, SF10
and NS10 occurred in the first step were 16.5%, 17.8%
and 18.5% respectively. This finding indicated the gradual
increase in hydrated mineral phases for FA10, SF10 and
NS10, where the highest percent of hydrated minerals was
found in NS10. The second step of decomposition of OPC
occurred between 325 °C and 550 °C, reached a maximum
rate at 432 °C, resulting in a 3.7% mass loss. The second step
of thermal decomposition of FA10, SF10 and NS10 occurred
in the same temperature range, where the corresponding
mass losses were 3.5%, 3.2% and 2.4% respectively. The
third decomposition step of OPC, as well as those of FA10,
SF10 and NS10, occurred between 550 °C and 740 °C. The
mass loss rates observed at the third step of DTG showed a
significant decrease in the rate of decomposition of calcium
carbonate in FA10, SF10 and NS10 in comparison to that of
OPC. The residues of FA10, SF10 and NS10 at 800 °C, as
well as the control were about 73-74% at early age.
Figure  6a and 6b show the TG–DTG behavior of all
the specimens after 28 days of curing. The significant
points of the TG–DTG analysis at the age of 28 days can
be summarized as follows: the incline of the first step of the
TG curve of NS10 was very steep, the corresponding mass
loss rate was the maximum (1.7 %.min–1) and reached 22.6%
mass loss at 200 °C, much greater than SF10, FA10 and OPC
due to the higher extent of C–S–H formation in NS10[29,37,38].
The mass losses at the second step of TG analyses for FA10,
SF10 and NS10, related to the decomposition of CH, were
4.4%, 4.0% and 3.4% respectively, which were all lower than
5.0% mass loss of OPC. The second thermal decomposition
step of NS10 and of SF10 occurred considerably slower
than those of OPC and FA10 as given in their DTG curves
(Figure 6b). In the third decomposition step between 550 °C
and 740 °C, the mass loss rate of NS10 observed was the
smallest among all the samples. Residues of OPC, FA10 and
SF10 at 800 °C were 74%, 75%, 74%, respectively, while
the residue of NS10 was 68%.
Mass percent of Ca(OH)2 and of CaCO3 calculated from
the second and the third steps of TG analyses for the mortar
specimens containing 10 wt% of NS, SF and FA at the age of

Figure 8. SEM images of the mortar specimens after 28 days of curing: a) OPC (control group), magnification x5,000; b) NS10,
magnification x15,000; c) SF10, magnification x5,000; d) FA10, magnification x5,000.
2014; 17(3) Comparative Study of the Characteristics of Nano Silica–, Silica Fume– and Fly Ash–Incorporated Cement Mortars
7 days and of 28 days are given in Table 3. As seen in Table 3,
at the age of 7 days, the mass percent of free CH, which did
not enter the pozzolanic reaction, in FA10 and SF10 were
calculated as 14.4% and 13.2%, both were very close to that
of OPC (15.2%). Alternatively, the amount of free CH of
NS10 was found the least among all the samples, i.e. 9.9%.
In addition, the total amount of CH and calcium carbonate of
NS10 was 17.4%, which was also the smallest among all the
samples. These findings indicated the noticeable increase in
the extent of bond formation between NS and free calcium
hydroxide compared to bond formation of SF or FA with
free CH at early age. At standard age, the amount of free
CH and the total amount of CH and calcium carbonate for
NS10 were calculated as 14.4% and 19.4% respectively.
Both were considerably less than those of FA10 and SF10,
indicating the rising extent of bonding between NS and free
CH in NS10 in comparison to bonding in FA10 and SF10,
and also suggesting the difficulty of CO2 penetration in
NS10 due to the strength of bond formation and compact
structure of NS10. These results are in good agreement with
FTIR results along with the higher compressive and flexural
strengths observed in NS10.
SEM analyses were used to study the influence of NS,
SF and FA on the microstructure of the OPC mortar. The
SEM images of the fracture surfaces of OPC, NS10, SF10
and FA10 after 7 days of curing are shown in Figure  7.
The fracture surface of the OPC sample is typical for a
cement mortar, displaying a heterogeneous distribution of
C–S–H and CH grains and needle–like ettringite crystals.
Some micro cracks are visible within the structure. The
SEM images of SF10 and FA10 after 7 days of curing are
similar and show condensed packing of cement hydration
products. The mineral particles SF or FA are arbitrarily
dispersed throughout the hydrated cement products. The
SEM images show CH and ettringite crystals between the
C–S–H crystals1,16,29,49,53,58. The SEM image of the fracture
surface of NS10 after 7 days illustrates a very condensed
mortar structure and a good dispersion of NS clusters
throughout the entire surface of hydrated cement products.
The CH grains of NS10 are less visible than those of OPC,
SF10 and FA10[49,52,59-61].
The SEM images of the fracture surfaces of OPC,
NS10, SF10 and FA10 after 28 days of curing are given in
Figure 8. The SEM images of OPC (Figure 8a), SF10 and
FA10 (Figure 8c and 8d) display all hydrated cementious
products including C–S–H. At the same time, deposits of
small and large CH crystals are dispersed in the hardened
cement mortars, which are often in OPC and are quite
occasional in FA10 and SF10. The SEM image of NS10
(Figure 8b) differs from the SEM images of OPC, SF10 and
FA10, where the texture of the hydration products is denser
and more compact. Large crystals of CH are not observed
all through the structure.
4. Conclusion
In the present study, the influence of high dosages of
nano silica (NS) 5 wt% and 10 wt%, on the mechanical and
structural properties of cement mortars at early (7th day) and
standard (28th day) curing ages were studied and compared
with the effects of equal amounts of the commercially used
579
pozzolanic mineral additives silica fume (SF) and fly ash
(FA). For dispersing NS, SF and FA particles in the mortar
specimens properly, the colloidal mixture of each mineral
additive in water was prepared by stirring at 15,000 rpm for
2 min prior to mixing with cement, fine aggregate, and the
amount of hyperplasticizer was added.
The compressive strengths developed in the mortar
specimens containing NS particles were found considerably
higher than those of the corresponding specimens of SF and
FA over and above the control at early and standard ages.
Parallel to the increase in the amount of NS from 5 wt% to
10 wt%, the increases in compressive strength at both ages
were observed. At standard age, the compressive strength of
the mortar specimen with 10 wt% NS was 84% higher than
that of the control, while the compressive strengths of the
specimens with 10 wt% SF and 10 wt% FA were only 44%
and 18% higher than that of the control. The increases in the
flexural strengths of the mortars with 5 wt% and 10 wt% NS
were also noticeable compared to the mortars with SF and
FA on top of the control at standard age of curing.
The SEM images evidenced that NS was acting as
nucleating agent for C–S–H gel formation from C3S and
C2S. Nucleation appeared to occur along the entire surface
of the NS particles, rather than at specific locations. FTIR
and TG-DTG results supported the SEM observations. FTIR
spectrum of the mortar with 10 wt% NS was the evidence
for the highest degree of polymerization C3S and C2S phases
with the formation of C–S–H phase compared to the mortars
with SF and FA. TG-DTG results are in good agreement with
FTIR results along with the highest compressive and flexural
strengths observed in NS10. The extent of pozzolanic
reactions was followed by monitoring the change in the
amount of calcium hydroxide and of calcium carbonate,
from the second and third steps of TG analyses, at early
and standard ages for the samples containing 10 wt% NS,
SF and FA. The amount of free CH and the total amount of
CH and calcium carbonate of the mortar with 10 wt% NS
were found the lowest among all the samples at both ages,
suggesting the highest degree of bond formation between
NS and calcium hydroxide.
Nano silica particles with the average size of 15 nm and
the immense surface area of 640 m2.g–1 should have plenty
of quantum sized pores and quantum sized tunnels, resulting
in a pronounced surface reactivity. Accordingly, nano silica
particles acted as nucleating agents and promoted hydration
of C3S and C2S to produce prominent amount of C–S–H
phase in comparison to silica fume and fly ash. Nano silica
particles also possessed numerous active sites on their vast
surfaces, such as broken Si–O– and Si– bonds, giving rise
to very high pozzolanic reactivity and noticeable increase in
the extent of bond formation with free calcium hydroxide.
Consequently, the use of nano silica can be assertively
suggested to improve the structural characteristics and
mechanical performance of cement mortars and concrete
when compared to SF and FA. NS containing cement
composites can be appropriate for many applications where
early compressive strength is required, such as concrete roof
tiles, masonry blocks, high strength mortars etc., and also
for applications where improvement of flexural strength is
essential especially for unreinforced cement composites
580
such as airport concrete pavements and roads for safely
distributing concentrated loads over wide areas. Prior to the
use of NS in concrete applications, further investigations
must be performed for understanding the effect of NS
on the permeability, water absorption, workability, long
term durability and creeping of concrete, as well as the
manufacturing, safety and handling issues of nano silica-
supplemented cement mixtures, industrial scale-up of the
laboratory processes and cost.
Moreover, determination of surface characteristics of
pure nano silica particles and nano silica added cement
pastes, such as surface area, surface roughness, pore volume,
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